Method for terminating a low temperature polymerization process



Patented May 15, 1951 METHGD FOR TERMINATING A LOW TEM- PERATURE POLYMERIZATION PROCESS Henry G. Schutze, Baytown, Tera, assig'nor, by

mesne assignments, to Standard Oil Development Company, Elizabeth, N. J a corporation of Delaware No Drawing. Application May 26, 1948, Serial No. 29,404

6 Claims.

This application is a continuation-in-part of U. S. Serial No. 726,232, filed February 3, 1947, and now abandoned.

The present invention is directed to an improved process for the polymerization of olefins in the presence of aFriedel-Crafts catalyst. More particularly, the invention is directed. to the low temperature polymerization of olefinic mixtures in the presence of a catalyst of the aforementioned type.

In its more specific aspects, the invention is concerned with the recovery of high molecular weight polymer from reactors in which it is produced.

' The production of high molecular weight polymer having the properties of synthetic rubber in volves the polymerization of a tertiary monoolefin, such as isobutylene, with a dioleiin, such as isoprene, or butadiene, at low temperatures :ol'f the order of 100 to -175 F. to obtain a product which has a small degree of unsaturation and.

susceptible to vulcanization. The polymerization is usually carried out at a low temperature in the aforementioned range in a diluent such as an alkyl halide, methyl chloride for example, with the reactant mass being well stirred and agitated throughout the course of polymerization. After the polymerization has reached a suitable point, the reactants are dumped into a body of a liquid such as hot water or alcohol to kill the reaction and to recover the synthetic rubber and unreacted hydrocarbons.

The aforementioned process has enjoyed commercial acceptance for a number of years but is still susceptible to many improvements. For example, after a period of operating time the synthetic rubber, a portion of which is quite tacky and adhesive, forms a film and deposits in lumps on the interior surfaces of the reactor and thus cuts down heat transfer and results in the reactors being shut down for cleaning. When 'a' reactor is shut down for cleaning, considerable amounts of valuable polymer remain in the contents of the reactor and ordinarily are lost by virtue of catalyst being present in activating quantities even though the flow of catalyst solution to the reactor may be stopped. Furthermore, when the contents of the reactor are displaced, this valuable polymer is discharged from the system which may result in a loss of from 1,000 to about 3,500 pounds of rubber. Also, by virtue of the fact that the catalyst is still active- 1y polymerizing the unsaturated material, a product is produced which may be deficient in quality and which contaminates the material remaining in the diluent which is of good quality.

It is, therefore, the main object of the present invention to provide a process whereby the valuable rubbery constituents remaining in the re-' actor at the termination of a run are recovered.

Another object of the present invention is to provide a process for shutting down a reactor in which synthetic rubber is produced whereby the reaction is terminated at the proper point and the product remaining inthe reactor is substantially recovered.

The objects of the invention are achieved by terminating the flow of catalyst to the reactor and killing the residual catalyst remaining in the reactant solution while maintaining the flow of hydrocarbon feed thereto to allow recovery of the product remaining in solution under substantially operating conditions.

In accordance with the present invention, when it is desirable to shut down a given reactor of a plurality of reactors, the catalyst solution flow to the reaction is terminated While allowing the flow of hydrocarbon thereto to be continued, while maintaining vigorous agitation of the contents of the reactor. A quantity of a reagent, such as isopropyl alcohol or other alcohols of the same homologous series, is added to the contents of the reactor which kills the activity of the catalyst. During all this time, the agitation of the reactor contents is continued and the how of hydrocarbon thereto as is in conventional operation with temperature conditions being maintained at a tem perature in the range mentioned above.

The present invention is based on the discovery that active catalyst is present in the reactor at all times during operation thereof. Hence, when a reactor run is terminated by cutting off the flow of catalyst to the reactor, the formation of high molecular weight polymer is not terminated by the lack of fresh catalyst. made in the quantity of feed conducted to the reactor after catalyst addition thereto has been terminated, the reactor will continue to produce rubber for an additional 30 to minutes. Since, in the operation of a commercial synthetic rubber polymerization plant, it is desirable to obtain maximum advantage of the recycle, refrigeration, and feed preparation units, maximum polymer recovery from the reactor is obtained by utilizing a one to two hour feed flushing period during which the normal feed rate is maintained on the reactor. In a system in which complete mixing is obtained and in which no additional polymer is made after the catalyst has been cut out of the reactor, one displacement or the reactor contents will .flush approximately 66% of the polymer contained in the reactor slurry out If no changes are of the reactor overflow. However, if reaction continues after catalyst addition has been terminated, one displacement of the reactor will flush out considerably less than the 66% of the polymer contained in the reactor plus the polymer produced during the displacement period.

Thus, in accordance with the present invention, it is desirable to kill the active catalyst in the reactor with isopropyl alcohol or some other catalyst inactivator which is reactive with Friedel- Crafts catalyst, exemplified by aluminum chlo' ride which has found commercial usage. By re.- acting the residual aluminum chloride with isopropyl alcohol, all of the time allotted for the flushing out of the reactor contents is utilized in displacing the polymer from the reactor.

It has been known to quench reactions of ole-- fins in the presence of Ffriedel-Crafts type catalyst at low temperatures by adding an alcohol to the'reaction mass. The prior art processes, however, have been concerned with the production of synthetic resins and in preventing the reaction of less reactive olefins in the material at higher temperatures. It has also been known to discontinue the addition of catalyst to a reaction zone in which tertiary mono-olefins and diolefins are polymerized to arrest the polymerization reaction. However, in the prior art processes discontinuance of the addition of catalyst does not necessarily stop the reaction since cata lyst remains in the reaction body. Thus, it has been necessary to dump the reaction body into a body of water or water containing an alcohol and the like to destroy the activity of the catalyst. The prior art has also taught the destruction of catalyst by discharging a polymerization body including tertiary mono-olefins and diolefins into a body of naphtha containing a low molecular weight alcohol. Thus, the prior art has had no teaching or knowledge of the deleterious effects of allowing the catalyst to continue its polymerization activity in the presence of olefins in the reaction zone.

It has also been taught that a liquid mixture containing polymer in contact with a wall of a reaction zone may be prevented from adhering thereto by allowing the exposed wall surface to be flushed by the reaction mixture. The arts have also been taught to add solvents for polymerization products to the reactant hydrocarbon and have also been taught to flush the inner walls of a reaction zone with a solvent to prevent adherence of polymer thereto.

In contrast to the prior art processes, the present invention does not contemplate production of resins nor does it contemplate employment of temperatures in excess of 100 F. Neither does the present invention concern itself with dumping the polymerization mass into a body of quenching fluid. Thus, the products producible when operating at a temperature lower than l F. and the products producible above this temperature are quite diiferent, one being of the resin type and the other being of rubbery type having elasticity and susceptibility to vulcanization. The present invention is concerned chiefly with stopping a polymerization reaction in a reaction zone and conditioning the body of material contained therein so that it may be properly recovered. In short, in contrast to prior art teachings, the present invention interposes a step prior to the usual quenching or killing step. For example, it has been taught to dump the contents of a polymerization reactor in which a tertiary mono-olefin and a diolefin are polymerized into a body of liquid to stop the polymerization reaction and to recover the unreacted materials. It is to be reiterated that my invention includes as a step in the aforementioned f process intermediate steps in which the flow of polymer has a lower specific gravity than the liquid in which'it is produced, in this instance methyl chloride and unreacted butylene or isoprene, it is possible to cream the reactor contents by stopping the agitator after one-half to one displacement of the reactor contents has been. achieved. a If such an operation were. attempted when active catalyst were present in the reactor, the creamed polymer would float to the. top of the reactor and might agglomerate tov a hard dense mass which would plug'the overflow from the reactor and prevent flushing of the contents thereof. However, after the catalyst has been killed by injection of isopropyl alcohol into the contents of the reactor, the creamed polymer will not 'agglomerate and may be flushed out of the reactor by the feed being continued to the reactor as described before.

By proceeding inaccordance with the present invention, it is possible to recover more than 50% of the polymer in the reactor at the end of catalyst injection. Heretofore, most of this polymer has been lost whereas in accordance with the present invention, the amount of polymers; lost may be reduced to 5% of that contained in the reactor slurry at the termination of the reactor run.

The type of reactor employed in the practice;

of the present invention should be one as described in U. S. Serial No. 665,618, filed April 27, 1946, now abandoned and U. S. Serial No. 534,366, May 5, 1944, now U. S. Patent 2,474,592, for Frederick A. Palmer in which the reactor is provided with suitable agitating means and means for refrigeration to compensate for heat released by the reaction. The reactor is also provided with an overflow device to remove the product as produced and to compensate for the feed being constantly injected thereto. A suitable means for injecting the isopropyl alcohol into the feed going into the reactor should also be provided. Usually a small pot connected to a port controlled by suitable valving arrange-- ment on the feed line will be suitable.

The amount of alcohol or other deactivating agent will vary depending on the quantity of catalyst employed. A reactor feeding 5 pounds of aluminum chloride and 10,000 pounds of feed per hour will require about 1.0 gallon of isopropyl alcohol to kill the active catalyst remaining in the reactor. While isopropyl alcohol has been mentioned as the deactivating agent, other reagents such as tertiary butyl alcohol and the like may be used. The molar ratio of the inactivator to the quantity of catalyst, for example, aluminum chloride, contained in the reactor should be in' the ratio of at least two moles of inactivator to one mole of aluminum chloridecontained in the reactor.

The creaming of the reaction contents may be obtained by suitable agitation after one- 5 tourth to.;one displacement: of ath'e .rreactor contents has been :obtained rafter the .icata'lyst :has

sheen-"killed. ".The c'flu'shingis then continued for If 1 the .temperatureis notimaintained'in this -low temperature trange, :pro'ducts .of Limpaire'd qualiwirmight result.

;In::order .:to .illustrate. further ith-e benei lcial: of =fects of :.the present:invention, inspections are *olfinsshavirigfi to .7 .carbon :atoms 'such 35s isopentylene, .isohexylen'e, and isoheptyleneimay be i-substituted .forlthe isobuty-lene but the latter is preferred. .Similarly, butadiene "and iisop'rene rhavebeen .mentioned as the .diolefin. It -'-will be understood that other diolefins.and especially the conjugated .diolefins -may be employed in the 'ipracticeof my invention. Those diolefin s-having .5 .to '7 carbon atoms as illustrated by @pen'tadien'e- ..1;3,.hexadiene-1,3, and heptadie'n'e-LB may Joe used in lieu of isoprene and butadiene-l 3. Isop'rene, however, will be thepreferred diolefin.

Methyl chloridehas been' mentioned as a diluentfor the 'reaction and as a solvent for the cat- :givenzin'theafollowing.tableiofrsynthetic rubber is alyst. It will be understood that other tdiluents -recovered:;from. a commercial reactor'in which and other-solvents may be used. For example, the catalyst 'contained htherein was Kille'dQby in ethyl chloride, rnethylbromide, carbon disulfide, ijection of Lisoproprylaalcohol-tat ithe "end 0f ."the carbon tetrachloride :and the like may be used rrun. .lnttheseiparticular .runsctheieed mixture .a'sdiluents.and'isolvents for the reaction. I

consisting cof 126.3% Lby :weight :of .isobutylene, 2 Aluminum 'chlorideihas been employed-in de- 10.71% lhy'zweightvisoprene,-:and: .73% iby' vveightof .sc'ribing the invention iaa's illustrative of the .methylcchloridetwas polymerized treat :a ltempe'r-a- Friedel-Crafts icatalyst. .It"'-wi1l be understood turednxthezrange :between i12'0 :and +1.40 .tha't'other "Friedel-Crafts catalysts such asferric hyza'ddition to ithefieedt'mixture :o'f Lia catalytic .chloridegtit'anium tetrachloride, zirconium chlosolution :of :saluminum fchloride-in'lmethyl :chlo- "g5 .rid'eyand th'e like;may-be'employedin thepra'ctice .rr-ide. LThe matalytic ;.so1ution :icontained 'ian of 'the present invention, but aluminum chloride "amount .or .ia'lum'inum chloride between .0.2 a nd Will'bezpreferred in view of its availability, cheap- 0i-3;% :weight .uo'f .athe :solutjion. Ihe .zsolu-tion :nes's, and the-experiencegained in handling it.

.was added -to :"thefeed mixturesatra =rate of 1 500 The feed mixtureqnay contain an amount of vpounds ofacatalyticasolution perlhour While the 0 diluent such as methyl'chlorid'e in the range from feed mixture was :added .to:thea eact-ioni zone at about 70m 80% by weight, tertiary mono-olefin auate aof -.10,000 .pounds per :hour. in the range betweenabout ='and by weight,

-55 32 2, 730 820 490 7'35 {075 54.7 :32 130 t 2,5570 790 555 855 1,145. 4515 .20 .25 2, 500. 830 535 700 1, 50v 15.0 54 '31 25840 780 520 005 1, 350 38. 0 135.5 .512 2,570 700 545 890 1, 100 35. 5 37 .33 2,550 7 5 .555 52 5 1, 220 49. 0 35. 5 34.5- 2,730- 515 500 000 I 1, 205 -41. 0 :10. 0. :33. 5. 2, 710 700 595 000; 1, 205 37.3 42; 0 30. 0 2,895 790 595 595 1,180 57. 4 --43; 0 40.5 2, 700 750 545 055 1,550- 13. 5 43.0 140:0. 2,805: 735 140 1,01 1,400 45.9 50.0 45. 5 010 760 705 1, 020 1,400 1035 52:5 29. 5* 2, 590 745 515 050 1,540 5 '28. 5 s7 :34 2; 500; 7:15 020 555 :1, 450 -35.;2 52 47 2, s75 750 650 1, 25 "1,500 20. 0 40 35 2,700 755 520 r 025 r 1, 330 19. 0 48. 0 -43. 5 2,505 705 5 0 055; 1,420; 7. 52. 5 5s. 0 r 2, 050 750 730 1, 075 1,495 7. 0 -15 41 2,810 750 :525- 955- 1,5115 14.5 32 20 550 840 520 7,0 0 1, 1o0 7.5 44.0 40. 5, 2, s50, 75 515 075 1,555 as. 5 414-5 37 2, 500- 750 505 055 1, 330 12. 0 143 40.5 2,500 7 '505. 1,015 1385 0.0.7 40 '2, 825 740 700 1, 020 1, 400 55.5 :25 21 2,250: 840 400 525 975 15. 5 35 32 2,750 785 500 035: 1,:1 25 28.0 '44 '39 2,730' 755 545 155' 1,520 21.5 21 10 2, 240 225 445 735 1,050 46. 0

,All compounds and tests in accordance with RubberflPe'ServeSpecificationProcedure forGii'L llanuafiy and diolefin from-about 0.3 to 019% by weight of the feed mixture. vA :feed mixture containing approximately 73% diluent, 26.5% 'of tertiary mono-olefin, and 0.5% of diol'efin gives very satis'factory results.

The reactor employed in the practice or the present 'inventio'n may be charged at a feed rate sufii'cient to provide an amount of diluent thereto in the range between 8400 and 9600 ounds :per hour, an amount of hydrocarbon imixtur'e including tertiary 'inono olefi'n and tii'olefin in the amounts in the range between 2000 and 3000 pounds per hour and aluminum chloride in the catalytic solution in an amount in the range between 2 pounds and 5 pounds per hour.

The alcohol employed to stop the reaction has been illustrated by isopropyl alcohol. It will be understood, of course, that other alcohols such as propyl alcohols, butyl alcohols, and the like may be used in lieu of isopropyl alcohol. In general, it will be desired to employ alcohols having 2to 5 carbon atoms in the molecule, such as ethyl alcohol, propyl alcohols, butyl alcohols, and amyl alcohols.

The nature and-objects of the present invention having been duly described and illustrated, what I wish to claim as new and useful and to secure by Letters Patent is:

l. A method forterminating the reaction between a tertiary mono-olefin and a diolefin in a reaction zone in which the tertiary mono-olefin and diolefin'are being polymerized ina diluent for the reaction at atemperature no greater than -.-l F. in the presenceof a solution of a Friedel-Crafts catalyst which consists of the steps of separately flowing said catalyst solution and said hydrocarbons in said. diluent to said reaction zone, maintaining the temperature in said reaction zone in the range between 100 and l75 FL, terminating the flow of catalyst solution to said reaction zone in which said tertiary mono-olefin and a diolefin are being polymerized in said diluent for the reaction, continuing the flow of said hydrocarbons in said diluent for the reaction to. said reaction zone, adding to the chilled hydrocarbons and diluent in the reaction zone an amount of a saturated aliphatic alcohol having-no more than carbon atoms in the molecule in the ratio of at least 2 mols of alcohol per mol of Friedel-Crafts catalyst in said reaction zone, and recovering the contents of the reaction zone by continuing to supply hydrocarbons and diluent thereto at a temperature in the range between 100 and l75 F. for a substantial length of time suffithe reaction zone.

2. A method for terminating the reaction between a tertiary mono-olefin and a diolefin in a reaction zone in which the tertiary mono-olefin and diolefin are being polymerized in a diluent for the reaction at a temperature no greater than -100 F. in the presence of a solution of a Friedel-Crafts catalyst under conditions of Violent agitation, which consists of the steps of separately flowing said catalyst solution and said hydrocarbons in said diluent to said reaction zone, maintaining the temperature in said reaction zone in the range between -100 and 175 3. A method for terminating the-reaction be,-

rtween a tertiary mono-olefin and a diolefin in a reaction zone in which the tertiary mono-olefin and diolefin are being polymerized in a diluent for the reaction at a temperature no greater than l00 F. in the presence of a solution of a Friedel-Crafts catalyst under conditions of Vi0; lent agitation which consists of the steps of separately flowing said catalyst solution and said hydrocarbons in said diluent to said reaction zone, maintaining the temperature in said reaction zone at a temperature in the rangebe tween 100 and -175' F., terminating. the flow of catalyst solution to said reaction zone in which said tertiary mono-olefin and a diolefin are being polymerized in a diluent for the-reaction, con.- tinuing the flow of said hydrocarbons in said diluent for the reaction to saidreaction 'zon'e while continuing the agitation in thereaction zone, adding to the chilled hydrocarbons and diluent, inthe reaction zone an amount of a saturated aliphatic alcohol having no more-than 5 carbon atoms in the molecule inrthe ratio .of'ii mols of alcohol per mol of Friedel-Craftscatalyst'in said reaction zone,.discontinuing agitation in thereaction zone, and recovering the contents of the reaction zone by continuing'to supply hydrocarbons and diluent thereto at a temperature in the range between l00 and -1'75 F. for a time sufficient to displace at least 4 of the contents of the reaction zone. II

4. A method for recovering a. high molecular weight polymer from a reaction zone in which a mixture, including an amount of isobutylene in the range between 20% and by weight,

isoprene in an amount in the range between 0.3% and 0.9% by weight, and methyl chloride in an amount in the range between 70% and F., terminating the flow of catalyst solution to said reaction zone in which said tertiary mono-- olefin and a diolefin are being polymerized-in a diluent for the reaction, continuing the flow of.

said hydrocarbons in said diluent for the reaction to said reaction zone while continuing agitation of the mixture of hydrocarbons and diluent in the reaction zone, adding to the chilled hydrocarbons and diluent in the reaction zone an amount of a saturated aliphatic alcohol having no more than 5 carbon atoms in the molecule in the ratio of at least 2 mols of alcohol per mol of Friedel-Crafts catalyst in said reaction zone, and recovering the contents of the reaction zone by continuing to supply hydrocarbon and diluent thereto at a temperature in the range between -100 and -175 F. for a substantial length of time sumcient to displace at least of the contents of the reaction zone.

% by weight, is being polymerized at a temperature in the range between and F. in presence of a solution. of aluminum chloride in methyl chloride under conditions of w cient to displace at least 4 of the contents of Violent agitation Which Consists Of s il flowing said aluminum chloride solution and said hydrocarbons in said methyl chloride to said re-. action zone, terminating the flow of aluminum chloride solution to said reaction zone in which said mixture .is being polymerized, continuing the flow of said feed mixture to the reaction zone while continuing agitation of the contents thereof, adding to the mixture in the reaction zone an amount of isopropyl alcohol sufiicient to provide 2 mols of isopropyl alcohol per mol ofaluminum chloride in the reaction zone, con,-' tinuing agitation of the contents of said reactionzone, and recovering the contents of said reactionv zone by continuing to supply feed mixture there-;

to at a temperature in the range between l20,

and --1l5 F. for a substantiallengthjof timef weight, is being polymerized at a temperature in the range between l20 and-145? F. in the presence of a solution of aluminumchloride in methyl chloride under conditions of violent agitation which consists of separately'iiowing said aluminum chloride solution and said hydrocarbons in said methyl chloride to said reaction zone, terminating the flow of aluminum chloride solution to said reaction zone in which said mixture is being polymerized, continuing the flow of said feed mixture to the reaction zone while continuing agitation of the contents thereof, adding to the mixture in the reaction zone an amount of isopropyl alcohol sufficient to provide 2 mols of isopropyl alcohol per mol of aluminum chloride in the reaction zone, discontinuing agitation of the contents of said reaction zone, and recovering the contents of said reaction zone by continuing to supply feed mixture thereto at a temperature in the range between 120 and -145 F. for a substantial length of time sufficient to displace at least A of the contents thereof.

6. A method for recovering a high molecular weight polymer from a reaction zone in which a mixture, including an amount of isobutylene in the range between and by weight, isoprene in an amount in the range between 0.3% and 0.9% by weight, and methyl chloride in an amount in the range between and by weight, is being polymerized at a temperature in the range between and F. in the presence of a solution of aluminum chloride in methyl chloride under conditions of violent agitation which consists of separately flowing said aluminum chloride solution and said hydrocarbons in said methyl chloride to said reaction zone, terminating the flow of aluminum chloride solution to said reaction zone in which said mixture is being polymerized, continuing the flow of said feed mixture to the reaction zone while continuing agitation of the contents thereof, adding to the mixture in the reaction zone an amount of isopropyl alcohol sufficient to provide 2 mols of isopropyl alcohol per mol of aluminum chloride in the reaction zone until to 1 displacement of the feed admixture in the reaction zone has been effected, discontinuing agitation in said reaction zone for a time sufficient to allow the contents of said reaction zone to coalesce in a suspension of fine particles of solids in said hydrocarbons and methyl chloride, continuing the flow of said feed mixture to said reaction zone at a temperature in the range between -l20 and 145 F. until to 2 displacements of the mixture has been made, and recovering the contents of said reaction zone.

HENRY G. SCHUTZE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,408,007 Thomas et al Sept. 24, 1946 2,433,025 Calfee et al. Dec. 23, 1947 2,455,665 Ford et al. Dec. 7, 1948 2,474,571 Brakeley et a1 June 28, 1949 

1. A METHOD FOR TERMINATING THE REACTION BETWEEN A TERTIARY MONO-OLEFIN AND A DIOLEFIN IN A REACTION ZONE IN WHICH THE TERITARY MONO-OLEFIN AND DIOLEFIN ARE BING POLYMERIZED IN A DILUENT FOR THE REACTION AT A TEMPERATURE NO GREATER THAN -100* F. IN THE PRESENCE OF A SOLUTION OF A FRIEDEL-CRAFTS CATALYST WHICH CONSISTS OF THE STEPS OF SEPARATELY FLOWING SAID CATALYST SOLUTION AND SAID HYDROCARBONS IN SAID DILUENT TO SAID REACTION ZONE, MAINTAINING THE TEMPERATURE IN SAID REACTION ZONE IN THE RANGE BETWEEN -100* AND -175* F., TERMINATING THE FLOW OF CATALYST SOLUTION TO SAID REACTION ZONE IN WHICH SAID TERTIARY MONO-OLEFIN AND A DIOLEFIN ARE BEING POLYMERIZED IN SAID DILUENT FOR THE REACTION, CONTINUING THE FLOW OF SAID HYDROCARBONS IN SAID DILUENT FOR THE REACTION TO SAID REACTIN ZONE ADDING TO THE CHILLED HYDROCARBONS AND DILUENT IN THE REACTION ZONE AN AMOUNT OF A SATURATED ALIPHATIC ALCOHOL PER MOL OF FRIEDEL-CRAFTS CATAATOMS IN THE MOLECULE IN THE RATIO OF AT LEAST 2 MOLS OF ALCOHOL PER MOL OF FRIEDEL-CRAFT CATALYST IN SAID REACTION ZONE, AND RECOVERING THE CONTENTS OF THE REACTIONS ZONE BY CONTINUING TO SUPPLY HYDROCARBONS AND DILUENT THERETO AT A TEMPERATURE IN THE RANGE BETWEEN -100* AND -175* F. FOR A SUBSTANTIAL LENGTH OF TIME SUFFICIENT TO DISPLACE AT LEAST 1/4 OF THE CONTENTS OF THE REACTION ZONE. 